Lubricating oil composition



Patented July 11, 1944 2,353,491 LUBBICATHWG OIL COMPOSITION Edward A. Oberright, Woodbury,

to Socony-Vacuum Oil Company,

N. J., assignor Incorporated,

a corporation of New York No Drawing. Application January 14, 1944,

Serial No. 518,260

18 Claims. (Cl. 252-51) This invention has to do in a general way with mineral oil compositions and is more par ticularly related to compositions comprised of mineral oil and a minor proportion of an added ingredient which will improve more important respects.

It is well known to those familiar with the art that mineral oil fractions refined for their var-' ious uses are in and of themselves usually deflcient in one or more respects so that their practical utility is limited even in the particular field for which-they have been refined. For example, mineral oil fractions refined for use as lubricants have a tendency to oxidize under conditions of use, with the formation of sludge or acidic oxidation products; also, the lighter fractions such as gasoline and kerosene tend to oxidize with the formation of color bodies, gum, etc. In order to prevent the formation of these products and thereby extend the useful life of the oil fraction, it is common practice to blend with suchoil fraction an additive ingredient which will inhibit oxidation, such ingredients being known to the trade as oxidation inhibitors, antioxidants, sludge inhibitors, gum inhibitors, etc.

It is also the practice to add other ingredients to mineral oil fractions for the purpose of improving oiliness characteristics and the wearreducing action of such mineral oils when they are used as lubricants, particularly when the oils are used for the purpose of lubricating metal surfaces which are engaged under extremely high pressures and at high rubbing speeds.

Various other ingredients have been developed I for the purpose of depressing the pounpoint of mineral oil fractions which have been refined for use as lubricants. Most refining treatments provide oils containing a small amount of wax which, without the added ingredient, would tend to crystallize at temperatures which render the oil impracticable for use under low temperature con ditions. Additive agents have also been developed for' improving the viscosity index of lubrieating all fractions. In the case of internal combustion engines, particularly those operating with high cylinder pressures, there is a decided tendency for the ordinary lubricating oil fractions to form carbonaceous deposits which cause the piston rings to become stuck in their slots and which fill the slots in the oil ring or rings, thus materially reducing the efficiency of the engine. Ingredients have been developed which, when added to the oil, will reduce this natural tendency of the oil to form deposits which interfere with the function of the piston rings.

It has also been discovered that certain types of recently-developed hard metal alloys, such as cadmium-silver alloy bearings, are attacked by the oil in one or 6 ingredients in certain types of oils, particularly oil of high viscosity index obtained by various methods of solvent-refining. This corrosive action on such alloys has led to the development of corrosion-inhibitors which may be used in solvent-refined oils to protect such bearing metals against this co osive action.

In the lighte mineral oil fractions, such as those'used for fuel purposes, particularly in internalcombustion engines, it has been found that the combustion characteristics of the fuel maybe controlled and improved by adding minor proportions of various improving agents thereto.

The various ingredients which have been develped for use in mineral oil fractions to improve such fractions in the several characteristics enumerated above are largely specific to their particular applications. Therefore, it has been the practice to add a separate ingredient for each of the improvements which is to be effected.

The present invention is predicated upon the discovery of a group or class of oil-soluble reaction products or compounds which, when added to mineral oil fractions in minor proportions, will improve the oil fractions in several respects. Although the present application is directed broadly to all mineral oil compositions, including both lubricating oils and fuel oil distillates, the invention is illustrated herein by the lubricating oil compositions, and for details concerning the preparation and improved properties of the fuel oil compositions contemplated by the present invention, reference is made to copending application Serial No. 427,592, filed January 21, 1942, in which I am a coinventor and of which the present application is a continuation-in-part.

The novel addition agents contemplated by this invention as multifunctional improvers for mineral oils are the condensation products of an aldehyde, an aliphatic polyamine in which each amino group is characterized by the presence of at least one hydrogen atom, and an alkyl-substituted hydroxyaromatic compound which have been further reacted to replace the hydroxyl hydrogen of the condensation product with a metal. Preferred-reaction products are those obtained by condensing about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic polyamine in which each aminogroup is characterized by the presence of at least one hydrogen atom andwith a quantity of an alkyl-substituted hydroxyaromatic compound sufiicient that the content of the hydroxyaromatic radical is about one mol equivalent; and subsequently reacting the condensation product with an alcohol solution of an alkaline earth metal oxide or alkaline earth metal hydroxide to replace the hydroxyl hydrogen of the alkyl-substituted hydroxyaromatic compound.

Aldehydes contemplated by the present invention are the aliphatic aldehydes, representative of which are formaldehyde and acetaldehyde, and the aromatic aldehydes, such as benzaldehyde. Preference, however, is given to the aliphatic aldehydes, formaldehyde being particularly preferred.

The aliphatic polyamines contemplated herein are those in which each amino group is characterized by the presence of at least one hydrogen atom. Such aliphatic polyamines may contain only primary amino groups, only secondary amino groups, or both primary and secondary amino groups. Of this class of amines, preference is given to the diamines in which two primary amino groups are attached to adjacent carbon atoms, and particular preference is given to ethylene diamine. Typical polyamines of the class described by the foregoing are ethylene diamine, propylene diamine and the other members of this homologous series. Representative hydroxyaromatic compounds contemplated by the present invention are phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol, phenylethylphenol, phenol resins. methylhydroxydiphenyl, guiacol, alpha and beta naphthol, alpha and beta methylnaphthol, tolylnaphthol, xylylnaphthol, benzylnaphthol, anthranol, phenylmethylnaphthol, phenanthrol, monomethyl ether of catechol, methoxyphenol, phenoxyphenol, anisole, beta naphthyl methyl ether, chlorphenol, and the like. Preference in general is to the monohydroxy phenols otherwise unsubstituted. particular preference being given to phenol and alpha and beta naphthol.

As described above, the hydroxyl hydrogen of the alkyl-substituted hydroxyaromatic group in the intermediate condensation product is replaced with its equivalent of metal. Any metal may be used the oxide or hydroxide of which (in alcohol solution, if necessary) can be reacted with the intermediate condensation product, or a salt of which can be reacted in alcohol solution with the sodium salt of the intermediate product. Among the metals contemplated for this purpose are: copper, beryllium, magnesium, calcium, strontium, barium, radium, zinc, cadmium, mercury, germanium, tin, lead, vanadium, chromium, manganese, iron, cobalt, nickel, ruthenium, palladium, platinum, aluminum, antimony, arsenic, bismuth, cerium, columbium, gallium, gold, indium, iridium, molybdenum, osmium, rubidium, selenium, tantalum, tellurium, thorium, titanium, tungsten, uranium, and zirconium. Preference is given to metals of the alkaline earth group, particularly to barium. As noted above, the metal is preferably introduced by reaction of its oxide or hydroxide with the intermediate condensation product. Where necessary, an alcohol solution of the Jxide or hydroxide is used. The metal salts can also be prepared by reacting the sodium salt of the intermediate product with an alcohol solution of a salt of the desired metal, such as stannous chloride, lead acetate, thorium nitrate, titanium tetrachloride, etc.

Alcohols suitable for the last-mentioned purposes are methanol, ethanol, etc.

Broadly, the alkyl groups contemplated by the present invention as substituents on the hydroxyaromatic compound are alkyl groups which will impart oil-solubility to the final product. Preferably, such alkyl substituents are long-chain, relatively-high-molecular-weight hydrocarbon groups having at least twenty carbon atoms. Particularly well-adapted for the purpose herein described are alkyl groups derived from petroleum wax, which is a predominantly straightchain aliphatic hydrocarbon of at least twenty carbon atoms. It will be obvious to those skilled in the art that the maximum number of oilsolubilizing alkyl groups is limited by the number of valences on the aromatic nucleus available for substitution. Naturally, the maximum number of such groups which can be attached to a single aromatic nucleus will vary as the nucleus is monoor poly-cyclic and as the nucleus is otherwise substituted.

The present application has been purposely directed to reaction products of the aforesaid preferred reactants for as yet the theory of reaction is not fully understood. Some evidence is availablefor example, quantitative analysis of the reaction product-to point to the presence of a major quantity of one compound. For instance, when typical reactants, such as a waxsubstituted phenol, formaldehyde, ethylene diamine, and barium oxide in alcohol solution, are reacted as hereinafter described, analysis indicates that the predominant product is:

Wax Wax Probably also present in the reaction product is a compound of the following type:

n n n u n l I l l l Ba0 N(.-(.-N

l l l H H n Wax The foregoing is for illustrative purposes only and is not to be construed as limiting the present invention to a theory of reaction because the present invention is directed primarily to reaction products obtained by interreaction of the reactants described herein as multifunctional improving agents for lubricating oils and the like.

As stated above, the general procedure for preparing the contemplated reaction products involves the interreaction of an alkyl-substituted hydroxyaromatic compound, an aliphatic aldehyde, and an aliphatic polyamine wherein the amino groups have at least one free hydrogen, and subsequent reaction or treatment of the product thus obtained to replace or substitute the hydroxyl hydrogen with metal. A typical, and also preferred, alkyl-substituted hydroxyaromatic compound which may be used is a wax-substituted'pheno wax-phenol. The term wax as used herein designates petroleum wax or aliphatic hydrocarbons or hydrocarbon groups of the type which characterize petroleum wax. These socalled "Wax substituents may be obtained by alkylation of the phenol or hydroxy-aromatic hydrocarbon with a relatively-high-molecularweight aliphatic hydrocarbon or mixture of such hydrocarbons (such as petroleum wax) by any EXAMPLE 1 A. Alkylation of phenol A paraflin wax melting at approximately 120 F. and predominantly comprised of compounds having at leasttwenty carbon atoms in their molecules is melted and heated to about 200 F., after which chlorine is bubbled therethrough until the wax has absorbed about 16 per cent of chlorine, such product having an average com- B. Formation of intermediate product One hundred atoms of wax-phenol (3-16) prepared according to the foregoing procedure were heated to fluidity, and 12.7 grams of a 69 per cent solution of ethylene diamine in water were .added thereto. To give a more fluid mixture about 100 cc. of butanol were also added. To. this solution 22.2 grams of a 3'1 per cent solution of formaldehyde in water were added dropwise. and the reaction was stirred 3% hours at 'room temperature and thenheated for 7 /2 hours at a reflux temperature of about 100 C. The reaction mixture was water-washed three times, and the solvent and entrained water were removed by distillation'to leave the aliphatic diamino-substituted wax-phenol reaction product.

C. Metalorgam'c reaction product I Twenty-fiv grams of the product obtained by the procedure described in paragraph B above were blended with 75 grams of mineral oil. Five position between a monochlor wax and a dichlor wax.- Preferably, the chlorination is continued until about one-sixth the weight of the chlorwax" formed is chlorine. A quantity of chlorwax thus obtained, containing three atomic proportions of chlorine, is heated to a temperature varying from just above its melting point to not over 150 F., and one 'mol of phenol (CsHsOH) is admixed therewith. The mixture is heated to about 150- R, and a quantity of anhydrous aluminum chloride corresponding to-about 3 per cent of the weight of chlorwax in the mixture is slowly added with active stirring. The rate of addition of the aluminum chloride should be sufllciently slow to avoid violent foaming, and during such addition the temperature should be held at about 150 F.

After the aluminum chloride has been added, the

may be increased 15 to minutes to temperature of the mixture slowly over a period of from a temperature of about 250 F. and then should be more slowly increased to about 350 F. To control the evolution of HCl gas the temperature of the mixture is preferably raised from 250 F. to 350 F. at a rate of approximately one degree per minute, the whole heating operation occupying approximately two hours from the time of adding the aluminum chloride. If the emission of HCl gas has not ceased when the final temperature is reached, the mixture may be held at 350 F. for a short time to allow completion of the reaction. However, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it be held at that temperature for any extended length of time.

It is important that all unreacted or non-alkylated hydroxyaromatic material (phenol) remaining after the alkylation reaction be removed. Such removal can be effected generally by wator-washing, but it is preferable to treat the water-washed product with superheated steam, thereby insuring complete removal of the unreacted material and accomplishing the drying of the product in the same operation.

.A wax-substituted phenol prepared according to the above procedure in which a quantity of chlorwax containing three atomic proportions of chlorine and having a chlorine content of 16 per cent is reacted with one mol of phenol will be hereinafter designated as wax-phenol (3-16). 76

grams of barium hydroxide octahydrate were added at room temperature. The temperature was slowly raised, and the water of crystallization and the water from th reaction were gradually distilled out. The reaction was held at 150- 200 C. for two hours an'dthen cooled. When cool, the reaction mixture was diluted with benzol and filtered through Hi-Flo clay to'remo've the unreacted barium hydroxide. removed by distillation under 20 mm. pressure, arid the final product was approximately a /4 mineral oil blend, which'wiil be hereinafter designated as Product one.

. "Exutrar'2' A. Alkylation ofphenol A paraffin wax melting at approximately 120 F. and predominantly comprised of compounds having at least twenty carbon atoms in their molecules was melted and heated to about 200 F.,

after which chlorine was bubbled therethrough according to the procedure followed in Example 1.

section A, except that the chlorination was continued until the wax had absorbed only about 14 per cent of chlorine. A quantity of chlorwax thus obtained, containing two atomic proportions of chlorine, was heated -to.a temperature varying from just above its melting point to not over' B. Formation of intermediate product One hundred'fifty grams of wax-phenol (2-14) prepared according to the foregoing procedure were heated to fluidity. and 20.8 grams of a 69 per cent-solution of ethylene diamine in water were added thereto. To give a more fluid mixture, about cc. of butanol were also added. To this solution 19.5 grams of a 37 per cent solution of formaldehyde in water were added dropwise, and the reaction was stirred 3 hours at room temperature and then heated for 7 /2 hours at a reflux temperature of about 100 C. The reaction mixture was water-washed three times, and the solvent and entrained water were removed by distillation to leave the aliphatic diamino-substituted wax-phenol reaction product.

C. Metalorganic reaction product Twenty grams of the product obtained by the The diluent was procedure described in paragraph Babove were blended with 40 grams of mineral oil, and 0.69 gram of sodium as sodium butylat'e were added thereto. A solution of 3.0 grams of stannous chloride in butanol was gradually added to the reaction mixture at room temperature, and then the reaction was held at the reflux temperature for one hour. The butanol was removed from the reaction mixture by distillation, and the product was filtered through Hi-Flo on a heatedfunnel to remove precipitated sodium chloride. ,The final product was approximately a 1/; mineral oil of chlorine, was heated to a temperaturevaryin'g from just above its melting point to not "over 150 F., and one mol of phenol (,CsHsQH) was admixed therewith. The mixture was.v thengsubjected to the procedure foliowedinfExample '1.

to give a wax-substituted phenol which 'willbe hereinafter designated as wax-phenol (2-12)."

B. Formation of intermediate product One hundred grams of wax-phenol (2-12)- prepared according to the torg'oingprocedure were heated to fluidity, and 7.45'grams ofj'a Go'per cent solution of ethylene diamine in water were'added thereto. 'For greater fluidity "about 100 cc. *of

butanol were also added. To thismixture 12.0-

grams of a 37 per cent solution of formaldehyde in water were addeddropwise, and the'reacti'on was stirred 3 /2 hours'at room temperaturefand then heated 7 /2 hours at a reflux temperature of about 100 C. The reaction mixture was waterwashed three times, and the solvent and entrained water were removed by distillation to obtain the final intermediate product, which was a /2 oil blend.

C. Metalorganic reaction product One hundred fiity grams of the product obtained by the procedure described in paragraph B, which as stated above. was a /2 oil blend, were heated to 75 C.. and 8.18 grams oi barium (as BaO) in methanol were gradually added. asthe methanol was allowed to distill 011. After all the barium oxide in methanol was added, the temperature was raised to 150 C. and held there to remove all of the methanol. The .product was filtered through Hi-Flo on a heated funnel, and the final product obtained, which wasapproximately a /2 oil blend, will be hereinafter designated as Product three.

EXAMPLE 4 A. Alkylation of phenol A paraflln wax melting at approximately 120 F. and predominantly comprised of compounds having at least twenty carbon atoms in their molecules was subjected to the procedure described in Example 1 except that chlorination of the wax was continued until it had absorbed only about 15 per cent of chlorine and that a quantity 01' this chlorwax containing only about two atomic proportions of chlorine was admixed with one mol of phenol. This product will be designated hereinafter as wax-phenol (215). B. Formation of intermediate product This product was obtained in the same'manner as the intermediate product of Example 1 except that the proportions of reactants used were difierent.

cent solution or formaldehyde in w'aterand 27.8

grams of a 69 per cent solution of ethylene diamine in water.

C. Metalorganic reaction product The procedure of Example 1 was also followed in this step except that here again the proportions of reactants used were different. Twentyfive grams of the product obtained above were blended with 75 grams of mineral oil, and 10.9 grams of barium hydroxide octahydrate were added thereto. The final product was approximately 9. A mineral oil blend and will be des the-'above-examples, when added to lubricating oils in minor proportions, have been found to improve these oils in several important respects.

This phenomenon is demonstrated by the following tables, which give the results of the various tests conducted to determine the effectiveness of Poua Pomr Dsrnsssron Tests were conducted in the conventional manner to determine the A. S. T. M. pour points of blends of these reaction products with 9. Mid- Continent solvent-refined oil of Saybolt Unversal viscosity of 67 second at 210 F. as compared with the pour point of the blank oil. The results given in Table I below demonstrate the effectiveness of the reaction products contemplated herein as pour point depressants.

VrscosrrY Iunsx IMPROVEMENT A mineral oil of 41.8 seconds Saybolt Universal viscosity at 210 F. was tested in the conventional manner to determine the improvement in viscosity index values efi'ected by various of the reaction products contemplated by this invention. This improvement is clearly demonstrated by the results set forth in Table II below.

Two hundred grams of wax-phenol (2-15) were reacted with 26 grams of a 37 per Table II Viscosity index values a Percent Addition a ent 4 g Mded Inhibited Uninhibited oil oil Product oue. l 90. 7 77. 7 Product two i 84.8 77.7 Product four 1 89.4 77.7

Coaaosioif'i'asr In this test the reaction product was blended with a Pennsylvania solvent-refined oil of Sayboit Universal viscosity of 53 seconds at 210 F., and a section of a bearing containing a cadmiumsilver alloy surface and weighing-about 6 grams was added tothis blend. The oil was heated to 175? C..for 22'hours while a stream of air was bubbledagainst the surface of the hearing. The

loss in weight or the bearing du'ringthis treat-' ment measured the amount ofcorrosion that had taken place. A sample of thestraight'oil was subjected to the same testat-the same time, and

the diflerence'between the losses-in weight of the two bearing sections demonstrated conclusively the effectiveness ofthe reaction products contemplated herein as corrosion-inhibitors.

' Sodom-Vacuum TURtrim-Tzsr I Twenty-five. cc. samples of a furfural--reflned Rodessa crude of Saybolt Universal viscosity-of 150 seconds at 100 F. and of a blend of this same oil and Product two were subjected to the following test to determine the effectiveness ofv the reaction products contemplated by this invention wa's'ca'rri'ed out'i'na single-cylinder CFR engine cooled with a vdiethylene glycol-water mixture held at a temperature of about 390 F. The engine'was operated continuously over a time interval of twenty-eighthours at a speed of about 1200 R. P. M., which is equivalent to a road speed of about 25 miles per hour. The oil temperature was held at about 150 F. during the test.

The conditions observed at the end of the test were: the extent to which the piston rings were stuck; the'extent to which the slots in the oil rings were filled with deposit; the amount of carbonaceous deposits in the oil; and the neutralization number '(N. N.) or acidity of the oil at the end of the test. Comparative runs were made with the oilalone and with the oil containing one per cent of Product three. Results of these runs are given'in Table .V below.

It will be apparent. from the foregoing data that the reaction products contemplated herein are effective notonly to inhibit corrosion and the various'effects ,of oxidation upon lubricating oils, such as formation of sludge and color bodies and other undesirable products, but also to depress the pour point and improve the viscosity index of as inhibitors for turbine oils: To each sample were added 1 gram of iron granules and 24 inches of 18 gauge copper wire. The samples were then heated to a temperature of 200 F. with 5 liters of air per hour bubbling therethrough- Two cc. of distilled water were added each day. The re suits of the tests which were made for color and acidity or neutralization number and amount of sludge formed after certain time intervals are set forth in Table IV below.

It will be noted that although 389 mgms. of sludge had been formed in the uninhibited oil at the end of only 162 hours, only 14 mgms. had been formed in the oil blend at the end of substantially the same length of time and only 127 mgms. had been formed in the inhibited oil at the end of 384 hours.

CF'R. Rmc-S'rrcxmo Tzsr This test was conducted with an oil of saybolt Universal viscosity of 120 seconds at 215 F. and

such oils.

The improved properties obtained and the de-. gree of improvement effected may be varied with the aldehyde, metal, polyamine, and aromatic constituents in the reaction products, as well as by the degree of alkylation of the hydroxyaromatic nucleus. As to the degree of alkylatiomit is important that the hydroxyaromatic nucleus be sufficiently alkyiated to provide a final reaction product soluble or "miscible" in the particular lubricating oil fraction with which it is to be blended: that is, a reaction product whic'h'will remain uniformly dispersed in the oil in sufficient amount to effect the desired improvement. The amount of improving agent to be used varies with the mineral oil or lubricating oil fraction with which it is blended and with the properties desired in the final oil composition. These reaction products may be added to mineral oils in amounts of from about .05 per cent to about 10 percent, but amounts of from about 0.5 per cent to about 3 per cent are preferred for the purposes of this invention.

It is to be understood that although I have de scribed certain preferred procedures which may be followed in the preparation of the novel reaction products contemplated herein as multifunctional addition agents for mineral oils and have indicated representative reactants for use in their preparation, such procedures and reactants are merely illustrative and the invention is not to be considered as limited thereto or thereby but includes within its scope such changes and modifications as fairly come within the spirit of the appended claims.

I claim: I

1. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a reaction product; obtained by first interreacting an aliphatic aldehyde, an aliphatic polyamine in which each amino group has at least one hydrogen atom, and an alkyl-substituted hydroxyaromatic compound wherein the alkyl substituent has a sumcient chain length to impart oil-solubility to the final product; and then substituting the hydroxyl hydrogen in the condensation product thus obtained with metal.

2. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-halt mol equivalent of an aliphatic polyamine in which each amino group has at least one hydrogen atom and with a sufliciency of an alkyl-substituted hydroxyaromatic compound such that the content of the hydroxyaromatic radical in the reaction mixture is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufiicient chain length to impart oil-solubility to the final product; and then reacting the condensation product obtained by the foregoing procedure with an alcohol solution of a compound selected from the group consisting of metal oxides and metal hydroxides, said alcohol solution containing an equivalent of metal to replace the hydroxyl hydrogen of the aforesaid condensation product.

'3. A mineral oil composition comprising a min eral oil having admixed therewith a minor proportion of a. reaction product obtained by 'first interreacting an aldehyde, an aliphatic polyamine in which each amino group has at least one hydrogen atom, and an'alkyl-substituted hydroxyaromatic compound wherein the alkyl substituent has a sufiicient chain'length to impart oil-solubility to the final product; and then substituting the hydroxyl hydrogen of the condensation product thus obtained with metal.

4. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor-proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-halt mol equivalent of an aliphatic polyamine in which each amino group has at least one hydrogen atom and with a quantity of an alkyl substituted hydroxyaromatic compound suflicient that the content of the hydroxyaromatic radical in the reaction mixture is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufilcient chain length to impart oil-solubility to the final product; and then reacting the condensation product obtained by the foregoing procedure with a, compound selected from the group consisting of metal oxides and metal hydroxides, said compound containing an equivalent of metal to replace the hydroxyl hydrogen of the aforesaid condensation product.

5. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic polyamine in which each amino group has at least one hydrogen atom and with a quantity of an alkyl substituted hydroxyaromatic compound sufficient that the content of the hydroxyaromatic radical n the reaction mixture is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufiicient chain length to impart oil-solubility to the final product; substituting the hydroxyl hydrogen in the condensation product thus obtained with sodium to form the sodium salt; and then reacting said sodium salt with an alcohol solution of another metal salt to form the corresponding salt 01' said last-mentioned metal.

6. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of formaldehydre with at least onehalf mol equivalent of an aliphatic polyamine in which each amino group has at least one hydrogen atom and with a quantity of an alkylsubstituted hydroxyaromatic compound suflicient that the content of .the hydroxyaromatic radical is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufficient chain length to impart oil-solubility to the final product; and then reacting the condensation product obtained by the foregoing procedure with an alcohol solution ofa compound selected from the group consisting of metal oxides and fnetal hydroxides, said alcohol solution containing an equivalent of metal to replace the hydroxyl hydrogen oi the aforesaid condensation Product.

7. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by firstinterreacting about one mol equivalent of an aliphatic aldehyde withat least one-half mol equivalentof an aliphatic polyamine in which each amino group has at least one hydrogen atom and with a quantity of an alkyl-substituted hydroxyaromatic compound sufilcient that the content of the hydroxyaromatic radical is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufiicient chain length to impart oilsolubilityto the final product; and then reacting the condensation product obtained by the foregoing procedure with an alcohol solution of a compound selected fromthe group consisting of alkaline-earth oxides and alkaline-earth hydroxides, said alcohol solution containing an equivalent of metal sufiicient'to replace the hydroxyl hydrogen of the aforesaid condensation 7 product.

8. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting an aliphatic aldehyde, an aliphatic polyamine in which each amino group has at least one hydrogen atom, and an alkylsubstituted hydroxyaromatic compound wherein the alkyl substituent has a sufllcient chain length to impart oil-solubility to the final product; and then substituting the hydroxyl hydrogen in the condensation'product thus obtained with barium.

9. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic polyamine in which each amino group has at least one hydrogen atom, and with a quantity of an alkyl-substituted hydroxyaromatic compound sufilcient that the content of the hydroxyaromatic radical is about one mol equivalent, the

alkyl substituent in the last-mentioned compound having a sufilcient chain length to impart oilsolubility to the final product; and then reacting the condensation product obtainedby the foregoing procedure with an alcohol solution of a compound selected from the group consisting of barium oxide and barium hydroxide, said-alcohol solution containing an equivalent of barium to replace the hydroxyl hydrogen of the aforesaid condensation product.

10. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one moi equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic polyamine in which each amino group has at least one hydrogen atom, and with a quantity of an alkylsubstituted hydroxyaromatic compound sufllcient that the content of the hydroxyaromatic radical is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufficient chain length to impart oil-solubility to the final product; and then reacting the condensation product obtained by the foregoing procedure with a compound selected from the group consisting of barium oxide and barium hydroxide, said compound containing an equivalent of barium to replace .the hydroxyl hydrogen of the aforesaid condensation product.

11. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic diamine in which each of the two amino groups has at least one hydrogen atom and the amino groups are attached to adjacent carbon atoms, and with a quantity of an alkyl-substituted hydroxyaromatic compound sufficient that the content of the hydroxyaromatic radical is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufiicient chain length to impart oil-solubility to the final product; and then reacting the condensation product obtained by the foregoing procedure with an alcohol solution of a compound selected from the group consisting of metal oxides and metal hydroxides, said alcohol solution containing an equivalent of metal to replace the hydroxyl hydrogen of the aforesaid condensation product.

14. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of ethylene diamine and with a quantity of an align-substituted hydroxyaromatic compound sumcient that the content of the hydroxyaromatic radical is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sufficient chain length to impart oil-solubility to the final product; and then reacting the condensation product obtained by the foregoing procedure with an alcohol solution of a compound selected from the obtained by first interreacting about one v.mol

one-half mol equivalent of an aliphatic diamine in which each amino group has at least one hydrogen atom, and with a quantity of an alkylsubstituted hydroxyaromatic compound suflicient that the content of the hydroxyaromatic radical is about one mol equivalent, the alkyl substituent in the last-mentioned compound having a sumcient chain length to impart oil-solubility to the final product; and then reacting the condensation product obtained by the foregoing procedure with an alcohol solution of a compound selected from the group consisting of metal oxides and metal hydroxides, said alcohol solution containing an equivalent of metal to replace the hydroxyl hydrogen of the aforesaid condensation product.

12. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained -by first inter-reacting about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic diamine having two primary amino roups attached to adjacent carbon atoms, and with a quantity of an alkyl-substituted hydroxyaromatlc compound sufilcient that the content of the hydroxyaromatic radical is about one mol equivalent, the

group consisting of metal oxides and metal hydroxides, said alcohol solution containing an equivalent of metal to replace the hydroxyl hydrogen of the aforesaid condensation product.

15. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic polyamine in which each amino group has at least one hydrogen atom and with a hydroxyaromatic compound substituted with at least one oilsolubilizing alkyl group having at least twenty carbon atoms, the said substituted hydroxyaromatic compound being present in an amount such that the content of the hydroxyaromatic radical in the reaction mixture is about one mol equivalent; and then reacting the condensation product obtained by the foregoing procedure allgvl substituent in the last-mentioned compound with an alcohol solution of a compound selected from the' group consisting of metal oxides and metal hydroxides, said alcohol solution containing an equivalent of metal to replace the hydroxyl hydrogen of the aforesaid condensation product.

16. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic poly amine in which each amino group has at least one hydrogen atom, and with a phenol substituted with a wax-alky1 group, said phenol beingpresent in an amount such that the content of the said phenol in the reaction mixture is about one mol equivalent: and then reacting the condensation product obtained by the foregoing procedure with an alcohol solution of a compound selected from the group consisting of metal oxides and metal hydroxides, said alcoholsolution containing an equivalent of metal to replace the hydroxyl hydrogen of the aforesaid condensation product. t 17. An improved lubricant composition comprising a lubricating oil having admixed therev amine in which each amino group has at leastone hydrogen atom, and with ah'ydroxyaromatic compound substituted with at least one oilsolubilizing allwl group having at least twenty carbon atoms, the said substituted bydroxy-aromatic compound being present in an amount such that the content of the hydroxyaromatic radical in the reaction mixture is about one mol equivalent; and then substituting the lLvdro'Xyl hydrogen inthe condensation productthus obtained with metal.

18. An improved lubricant composition comprising a lubricating oil having admixed therewith a minor proportion of a reaction product obtained by first interreacting about one mol equivalent of an aliphatic aldehyde with at least one-half mol equivalent of an aliphatic polyaniine in which each amino group has at least one hydrogen atom, and with a phenol substituted with a wax-'alk'y1 group, said phenol bein'gpresent in an amount such that the content of the said phenol in the reaction mixture is about one mol equivalent; and thensubstituting the hydroxyl hydrogen in the condensation prodnot thus obtained with metal.

DWARD a opmmm.

cmFIcAm or conmgcnox. Pintentilo. 2, 53,191. July 11, 191 1 1mm: A. oaxmuaa'r.

It is hereby certified that ei'rer appears in the printed specification .0! the'above numflered patent'requiri'ng correction follows: Page 3,100-

ond column, line-2, for "items" read --grme-; and that the acid. Letters Patent should be read with this correction therein that, the same no; conr'om w the record ofthe case in the Patent Office.

Signed and sealed this 16111 da of January, A. D. 1915.

Leslie Frazer (Seal) 7 Q Acting Commissioner of Patents. 

